U.S. patent number 4,282,335 [Application Number 06/134,136] was granted by the patent office on 1981-08-04 for high molecular resin composition.
This patent grant is currently assigned to Mitsubishi Gas Chemical Company, Inc.. Invention is credited to Masanobu Masu, Zenpei Mizutani, Yukio Sasaki, Akitoshi Sugio.
United States Patent |
4,282,335 |
Sugio , et al. |
August 4, 1981 |
High molecular resin composition
Abstract
A high molecular resin composition having superior impact
strength and processability and comprising a polymeric matrix
containing polyphenylene ether and a minor proportion of a
low-molecular-weight olefin oligomer dispersed therein.
Inventors: |
Sugio; Akitoshi (Ohmiya,
JP), Masu; Masanobu (Tokyo, JP), Sasaki;
Yukio (Tokyo, JP), Mizutani; Zenpei (Tokyo,
JP) |
Assignee: |
Mitsubishi Gas Chemical Company,
Inc. (Tokyo, JP)
|
Family
ID: |
12485863 |
Appl.
No.: |
06/134,136 |
Filed: |
March 26, 1980 |
Foreign Application Priority Data
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Mar 30, 1979 [JP] |
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54/37016 |
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Current U.S.
Class: |
525/68; 525/132;
525/76; 525/80; 525/84; 525/93; 525/98 |
Current CPC
Class: |
C08L
71/123 (20130101); C08L 71/123 (20130101); C08L
2666/04 (20130101) |
Current International
Class: |
C08L
71/12 (20060101); C08L 71/00 (20060101); C08L
061/04 () |
Field of
Search: |
;525/68,69,76,80,84,85,92,93,104,106,98 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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42-7069 |
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Mar 1967 |
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JP |
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42-22069 |
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Oct 1967 |
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JP |
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43-17812 |
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Jul 1968 |
|
JP |
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47-32731 |
|
Aug 1972 |
|
JP |
|
Primary Examiner: Ziegler; J.
Attorney, Agent or Firm: Wenderoth, Lind & Ponack
Claims
What we claim is:
1. A high molecular resin composition comprising
(1) 97 to 99.9% by weight of a polymeric matrix containing
polyphenylene ether, and
(2) dispersed therein, 0.1 to 3% by weight of an olefin oligomer
having a number average molecular weight of not more than about
10,000.
2. The resin composition of claim 1 wherein said polymeric matrix
is polyphenylene ether.
3. The resin composition of claim 1 wherein said polymeric matrix
contains polyphenylene ether and a polystyrene resin or a rubbery
polymer.
4. The resin composition of claim 1 wherein said polymeric matrix
contains polyphenylene ether and not more than 95% by weight, based
on the polymeric matrix, of a polystyrene resin.
5. The resin composition of claim 4 wherein said polymeric matrix
contains polyphenylene ether and not more than 80% by weight, based
on the polymeric matrix, of a polystyrene resin.
6. The resin composition of claim 1 wherein said polymeric matrix
contains polyphenylene ether and not more than 20% by weight, based
on the polymeric matrix, of a rubbery block copolymer of the
following formula
wherein A and A' are identical or different, and represent blocks
of a polymerized vinyl aromatic hydrocarbon, and B is a block of a
polymerized conjugated diene monomer.
7. The resin composition of claim 6 wherein the proportion of said
rubbery block copolymer of formula (I) is not more than 10% by
weight based on the weight of the polymeric matrix.
8. The resin composition of claim 1 wherein the polymeric matrix
contains polyphenylene ether and not more than 20% by weight, based
on the polymeric matrix, of a rubbery block copolymer of the
following formula
wherein A and A' are identical or different and represent blocks of
a polymerized vinyl aromatic hydrocarbon, and B' is a block of a
hydrogenated polymer of a conjugated diene monomer.
9. The resin composition of claim 8 wherein the amount of the
rubbery block copolymer of formula (II) is not more than 10% by
weight based on the weight of the polymeric matrix.
10. The resin composition of claim 6 wherein said polymeric matrix
contains polyphenylene ether, not more than 80% by weight, based on
the polymeric matrix, of a polystyrene resin, and not more than 10%
by weight, based on the polymeric matrix, of the rubbery block
copolymer of formula (I).
11. The resin composition of any one of claims 1 to 10 wherein said
polyphenylene ether is a homopolymer of a structural unit of the
following formula ##STR4## wherein R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 are identical or different, and each represents hydrogen,
halogen, a hydrocarbon group, a cyano group, an alkoxy group, a
phenoxy group or a nitro group, or a copolymer containing said
structural unit.
12. The resin composition of claim 11 wherein said polyphenylene
ether is a poly-2,6-dialkyl-1,4-phenylene ether, which is a
homopolymer of the structural unit of formula (III) in which
R.sup.1 and R.sup.2 are alkyl groups and R.sup.3 and R.sup.4 are
each hydrogen.
13. The resin composition of claim 12 wherein said polyphenylene
ether is poly-2,6-dimethyl-1,4-phenylene ether.
14. The resin composition of claim 12 wherein said polyphenylene
ether is poly-2,6-diethyl-1,4-phenylene ether.
15. The resin composition of claim 11 wherein said polyphenylene
ether is a copolymer of a 2,6-dialkylphenol and a
2,3,6-trialkylphenol, which is a copolymer composed of a structural
unit of formula (III) in which R.sup.1 and R.sup.2 are alkyl groups
and R.sup.3 and R.sup.4 are each hydrogen, and a structural unit
for formula (III) in which R.sup.1 and R.sup.2 and R.sup.3 are
alkyl groups and R.sup.4 is hydrogen.
16. The resin composition of claim 15 wherein said polyphenylene
ether is a copolymer of 2,6-dimethylphenol and
2,3,6-trimethylphenol.
17. The resin composition of claim 1 wherein said olefin oligomer
is an oligomer of a vinyl olefin monomer.
18. The resin composition of claim 1 or 17 wherein said olefin
oligomer is at least one member selected from the group consisting
of
(a) a homo-oligomer of ethylene, propylene or butylene,
(b) a co-oligomer of at least two of the monomers in (a) with each
other, and
(c) a halogenated oligomer resulting from the halogenation of said
homo-oligomer (a) or co-oligomer (b).
19. The resin composition of claim 18 wherein said olefin oligomer
is homo-oligoethylene.
20. The resin composition of claim 18 wherein said olefin oligomer
is homo-oligopropylene.
21. The resin composition of claim 18 wherein said olefin oligomer
is a co-oligomer of ethylene and propylene.
22. The resin composition of any one of claims 1, 17 and 19 to 21
wherein said olefin oligomer has a number average molecular weight
of about 1,000 to about 10,000.
23. The resin composition of any one of claims 1, 17 and 19 to 21
wherein the proportion of said olefin oligomer is 0.1 to 1% by
weight.
24. The resin composition of claim 4 or 5 wherein said polystyrene
resin is a homopolymer of a structural unit of the following
formula ##STR5## wherein R.sup.5 is hydrogen or an alkyl group, X
is halogen or an alkyl group, and m is 0 or an integer of 1 to 5,
or a copolymer containing at least 25 mole% of said structural
unit.
25. The resin composition of claim 24 wherein said polystyrene
resin is at least one resin selected from the group consisting
of
(a) a homopolymer of styrene, .alpha.-methylstyrene, vinyltoluene
or nuclearly chlorinated styrene,
(b) a copolymer of at least two of the monomers in (a) with each
other,
(c) a copolymer of at least one of the monomers in (a) and at least
one mono-vinyl monomer other than the monomers in (a),
(d) a copolymer of at least one of the monomers in (a) and at least
one conjugated diene monomer, and
(e) a copolymer of at least one of the monomers in (a), at least
one mono-vinyl monomer other than the monomers in (a), and at least
one conjugated diene monomer.
26. The resin composition of claim 25 wherein said polystyrene
resin is homopolystyrene.
27. The resin composition of claim 25 wherein said polystyrene
resin is rubber-modified high impact polystyrene which is a blend
of polystyrene and styrene-grafted polybutadiene.
28. The resin composition of claim 25 wherein said polystyrene
resin is at least one styrene copolymer selected from the group
consisting of styrene-acrylonitrile copolymer, styrene-butadiene
copolymer, styrene-ethylene copolymer, styrene-propylene copolymer,
styrene-methyl methacrylate copolymer, styrene-isoprene copolymer,
styrene-chloroprene copolymer, styrene-butadiene-acrylonitrile
copolymer and ethylene-propylene-butadiene-styrene copolymer.
29. The resin composition of claim 6 or 7 wherein in formula (I), A
and A' represent a block of a polymer of at least one aromatic
vinyl monomer selected from the group consisting of styrene,
.alpha.-methylstyrene, vinyltoluene, vinylxylene and
vinylnaphthalene, and B represents a block of a polymer of at least
one conjugated diene monomer selected from the group consisting of
butadiene, isoprene, 1,3-pentadiene and 2,3-dimethylbutadiene.
30. The resin composition of claim 29 wherein in formula (I), A and
A' are polystyrene blocks and B is a polybutadiene block.
31. The resin composition of claim 8 or 9 wherein in formula (II),
A and A' represent a block of a polymer of at least one aromatic
vinyl monomer selected from the group consisting of styrene,
.alpha.-methylstyrene, vinyltoluene, vinylxylene and
vinylnaphthalene, and B' is a polymer block obtained by
polymerizing at least one conjugated diene monomer selected from
the group consisting of butadiene, isoprene, 1,3-pentadiene and
2,3-dimethylbutadiene, and hydrogenating the polymer.
32. The resin composition of claim 31 wherein in formula (II), A
and A' are polystyrene blocks, and B' is a hydrogenated
polybutadiene block.
33. The resin composition of claim 18 wherein said olefin oligomer
has a number average molecular weight of about 1,000 to about
10,000.
34. The resin composition of claim 18 wherein the proportion of
said olefin oligomer is 0.1 to 1% by weight.
35. The resin composition of claim 22 wherein the proportion of
said olefin oligomer is 0.1 to 1% by weight.
36. The resin composition of claim 1 wherein said olefin oligomer
has a number average molecular weight of about 1,000 to about
5,000.
Description
This invention relates to a high molecular resin composition
containing polyphenylene ether. More specifically, this invention
relates to a high molecular resin composition having superior
impact strength and processability and comprising a polymeric
matrix containing polyphenylene ether and a minor proportion of a
low-molecular-weight olefin oligomer dispersed therein.
Polyphenylene ether generally has superior mechanical properties,
but its moldability is poor. Furthermore, its superior impact
resistance as one mechanical property is slightly inferior to
certain other polymers, and it is desirable to improve such
properties.
In an attempt to improve the moldability of polyphenylene ether,
methods involving blending polyphenylene ether with polystyrene
have previously been suggested (see U.S. Pat. No. 3,383,435, and
Japanese Patent Publications Nos. 22069/67 and 17812/68). The
resulting blend exhibits improved moldability over the
polyphenylene ether, but its impact resistance is not entirely
satisfactory.
Accordingly, in order to improve the impact strength of
polyphenylene ether to a satisfactory level, methods involving
blending polyphenylene ether with a rubbery high-molecular-weight
polymer have also been suggested in the past (see U.S. Pat. Nos.
3,660,531 and 3,994,856, and Japanese Patent Publication No.
32731/72). The resulting blend shows improved impact strength over
the polyphenylene ether, but since the rubbery polymer increases
the melt viscosity of the blend, the moldability of the blend
becomes poor. If a large amount of the rubbery polymer is blended
in an attempt to improve impact strength further, the load exerted,
for example, on the screw in extrusion molding increases, or the
flowability of the resin in the mold becomes low in injection
molding. In either case, the poor moldability of the blend causes a
reduction in productivity.
A method has also been suggested which comprises blending
polyphenylene ether with a polyolefin in order to improve the
impact strength of the polyphenylene ether. Such a method is
disclosed in U.S. Pat. No. 3,361,851 and Japanese Patent
Publication No. 7069/67. Unlike the aforesaid conventional methods,
this prior method is an attempt to cause the blend to exhibit the
advantages of both the polyphenylene ether and the polyolefin.
Polypropylene or polyethylene used as a raw material for such
molded articles as films or sheets is a high-molecular-weight
polyolefin having an average molecular weight of at least about
40,000 and an Izod impact strength of 0.5 to several tens of
ft-lb/inch. Thus, this method is intended to afford a blend which
exhibits the advantages of both the polyphenylene ether and the
high-molecular-weight polyolefin having such a high impact strength
by blending the polyphenylene ether and the polyolefin within
quantitative ranges which maintain the compatibility of the
two.
The present inventors made investigations in order to find a high
molecular resin composition having quite a different chemical
composition from those of conventional compositions, and which
exhibits improved impact strength and moldability without impairing
the various inherent properties of polyphenylene ether. These
investigations have led to the discovery that when a minor
proportion of a low-molecular-weight olefin oligomer is blended
with polyphenylene ether, a high molecular resin composition having
excellent impact strength and processability is obtained without
impairing the excellent inherent properties of polyphenylene ether.
This discovery is surprising in view of the fact that the
low-molecular-weight olefin oligomer is a brittle wax-like solid
easily disintegrable by hand upon solidification after melting, and
shows only those properties which are unacceptable as molding
materials.
Accordingly, the present invention, in its broadest concept,
provides a high molecular resin composition comprising
(1) 97 to 99.9% by weight of a polymer matrix containing
polyphenylene ether, and
(2) dispersed therein, 0.1 to 3% by weight of an olefin oligomer
having a number average molecular weight of not more than about
10,000.
In the present invention, the polymer matrix containing
polyphenylene ether denotes a matrix consisting only of
polyphenylene ether, and a matrix consisting of a mixture of
polyphenylene ether and, for example, a polystyrene-type resin
and/or a rubbery polymer. Furthermore, as described hereinbelow,
this polymeric matrix may contain plasticizers, etc. as required
according to the purpose of use of the final resin composition.
The polyphenylene ether used in this invention is a homopolymer
composed of structural units expressed by the following formula
##STR1## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
identical or different, and each represents hydrogen, halogen, a
hydrocarbon group, a cyano group, an alkoxy group, a phenoxy group,
or a nitro group, and copolymers including the aforesaid structural
units.
In the definition of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in
formula (III), the halogen is, for example, fluorine, chlorine
and/or bromine, and chlorine is preferred. The hydrocarbon group
denotes, for example, an alkyl, alkenyl, aryl or aralkyl group.
Alkyl groups are preferred, and lower alkyl groups having 1 to 3
carbon atoms, such as methyl, ethyl or propyl, are especially
preferred. The alkoxy group denotes a lower alkoxy group having 1
or 2 carbon atoms such as methoxy or ethoxy.
Specific examples of the polyphenylene ether include homopolymers,
for example poly-2,6-dialkyl-1,4-phenylene ethers such as
poly-2,6-dimethyl-1,4-phenylene ether,
poly-2,6-diethyl-1,4-phenylene ether or
poly-2,6-dipropyl-1,4-phenylene ether, 2,6-diaryl-1,4-phenylene
ethers such as poly-2,6-diphenyl-1,4-phenylene ether, and other
homopolymers such as poly-2-methyl-6-chloro-1,4-phenylene ether and
poly-2-methoxy-6-methyl-1,4-phenylene ether; and copolymers
composed of a structural unit of formula (III) in which R.sup.1 and
R.sup.2 are alkyl groups and R.sup.3 and R.sup.4 are each hydrogens
and a structural unit of formula (III) in which R.sup.1, R.sup.2
and R.sup.3 are all alkyl groups and R.sup.4 is hydrogen, i.e. a
copolymer of a 2,6-dialkylphenol and a 2,3,6-trialkyl phenol, such
as a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol.
Among these poly-2,6-dialkyl-1,4-phenylene ethers and a copolymer
of a 2,6-dialkylphenol and a 2,3,6-trialkylphenol are preferred.
Especially preferred are poly-2,6-dimethyl-1,4-phenylene ether,
poly-2,6-diethylphenylene ether, and a copolymer of
2,6-dimethylphenol and 2,3,6-trimethylphenol. Above all,
poly-2,6-dimethyl-1,4-phenylene ether and a copolymer of
2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred.
Methods for producing such polyphenylene ethers are well known, and
for example, they can be obtained by oxidative coupling of the
corresponding phenols.
It has now been discovered that the impact strength and moldability
of the polyphenylene ether polymer or copolymer can be improved by
including a specified small proportion of an olefin oligomer having
a low molecular weight specified below in such a polymer or
copolymer.
It has also been found in accordance with this invention that when
an olefin oligomer having a specified molecular weight is included
in a matrix consisting of a mixture of polyphenylene ether and a
polystyrene resin and/or a rubbery polymer, the impact strength and
moldability of the polymer matrix can be similarly improved.
Thus, according to another aspect of this invention, there is
provided a high molecular resin composition comprising 97 to 99.9%
by weight of a polymer matrix containing polyphenylene ether and a
polystyrene resin and/or a rubbery polymer, and dispersed therein,
0.1 to 3% by weight of an olefin oligomer having a number average
molecular weight of not more than about 10,000.
The rubbery polymer is preferably a rubbery block copolymer. The
polystyrene-type resin can be incorporated in the polymeric matrix
in an amount of not more than 95% by weight, preferably not more
than 80% by weight, based on the polymeric matrix. The rubbery
block copolymer can be incorporated in the polymeric matrix in an
amount of not more than 20% by weight, preferably not more than 10%
by weight.
The polystyrene-type resin that may be included in the polymeric
matrix is, for example, a homopolymer having a structural unit of
the following formula ##STR2## wherein R.sup.5 is hydrogen or an
alkyl group, X represents halogen or an alkyl group, and m is 0 or
an integer of 1 to 5, or a copolymer containing at least 25 mole%,
preferably at least 30 mole%, of the above structural unit.
In formula (IV), the alkyl groups for R.sup.5 and X, independently
from each other, represent methyl, ethyl, propyl, etc. Of these,
methyl is especially preferred. The halogen for X is, for example,
fluorine, chlorine, bromine, etc. Chlorine is especially
preferred.
The homopolymer having the structural unit of formula (IV) is, for
example, a homopolymer of a styrene monomer of the following
formula ##STR3## wherein R.sup.5, X and m are as defined in formula
(IV), such as styrene, .alpha.-methylstyrene, vinyltoluene or
nuclearly chlorinated styrene.
Examples of the copolymers having at least 25 mole% of the
structural unit of formula (IV) are copolymers of the styrene
monomers of formula (IV') with each other, and copolymers of at
least one styrene monomer of formula (IV') with at least one other
mono-vinyl monomer and/or a conjugated diene monomer. Examples of
the mono-vinyl monomers other than the styrene monomers of formula
(IV') are ethylene, propylene, acrylonitrile, and methyl
methacrylate. Examples of the conjugated diene monomers are
butadiene, isoprene and chloroprene.
The aforesaid styrene copolymers may be any of random copolymers
and graft copolymers if they contain at least 25 mole%, preferably
at least 30 mole%, of the structural unit of formula (IV).
Examples of the polystyrene resins used in this invention include
polystyrene, graft copolymers (e.g., styrene-grafted polybutadiene
rubber resulting from graft copolymerization of polybutadiene with
styrene), a blend of polystyrene and styrene-grafted polybutadiene,
a random copolymer of styrene and acrylonitrile (to be written as a
styrene-acrylonitrile copolymer; the same manner of writing applies
to the following exemplification), a styrene-butadiene copolymer, a
styrene-ethylene copolymer, a styrene-propylene copolymer, a
styrene-methyl methacrylate copolymer, a styrene-isoprene
copolymer, a styrene-chloroprene copolymer, a
styrene-butadiene-acrylonitrile copolymer, and an
ethylene-propylene-butadiene-styrene copolymer.
Among the above polystyrene resins, polystyrene, and a blend of
polystyrene and styrene-grafted polybutadiene in which the latter
is dispersed in the former (known as rubber-modified high impact
polystyrene) are especially preferred.
The polystyrene resin may be included in the polymeric matrix in an
amount of not more than 95% by weight, preferably not more than 80%
by weight, based on the polymeric matrix. Within such a weight
range, the advantages of the polyphenylene ether and the
polystyrene resin can be retained in a well balanced condition.
A rubbery polymer is another polymer which may be included in the
polymeric matrix of this invention. The rubbery polymer may be any
of homopolymers, random copolymers or block copolymers of
conjugated dienes, monolefins, alkylene oxides, etc. Examples of
the homopolymers or random copolymers include so-called rubbery
polymers such as polybutadiene, polyisoprene, polychloroprene, an
ethylene-propylene-diene copolymer and polyisobutylene, and
polyalkylene ethers such as polyethylene oxide, polypropylene oxide
and polyepichlorohydrin.
Copolymers, particularly rubbery block copolymers, of dienes such
as butadiene and vinyl aromatic hydrocarbons such as styrene are
preferred for use in this invention.
Examples of such rubbery block copolymers include block copolymers
of the following formula
wherein A and A' are identical or different, and represent blocks
of polymerized vinyl aromatic hydrocarbon monomers, and B is a
block of a polymerized conjugated diene monomer, and block
copolymers of the following formula
wherein A and A' are as defined above, and B' is a block of a
conjugated diene monomer polymerized and hydrogenated.
In the formulae (I) and (II) above, the block of a polymerized
vinyl aromatic hydrocarbon monomer for A and A' denotes a
homopolymer or copolymer block obtained by polymerizing at least
one vinyl aromatic hydrocarbon monomer such as styrene,
.alpha.-methylstyrene, vinyltoluene, vinylxylene or
vinylnaphthalene. The block of a polymerized conjugated diene
represented by B in formula (I) denotes a homopolymer or copolymer
block obtained by polymerizing at least one conjugated diene
monomer such as butadiene, isoprene, 1,3-pentadiene and
2,3-dimethylbutadiene.
The block of a conjugated diene monomer polymerized and
hydrogenated which is represented by B' in formula (II) denotes a
block obtained by hydrogenating the aforesaid homopolymer or
copolymer block of conjugated diene monomer to reduce the degree of
unsaturation of such a block.
The method for producing the rubbery block copolymers used in this
invention is well known to those skilled in the art.
Among the above rubbery block copolymers, preferred are rubbery
block copolymers of formula (I) in which both A and A' are
polystyrene blocks and B is a polybutadiene block, and rubbery
block copolymers of formula (II) in which A and A' are polystyrene
blocks and B' is a hydrogenated polybutadiene block.
The rubbery block copolymer may be included in the polymeric matrix
in an amount of not more than 20% by weight, preferably not more
than 10% by weight, based on the polymeric matrix.
When the content of the rubbery block copolymer exceeds 20% by
weight, the rigid strength of the high molecular resin composition
decreases, and the flowability of the resin composition during
melting tends to decrease.
It is also possible in this invention to include both the aforesaid
polystyrene resin and the aforesaid rubbery polymer, preferably the
rubbery block copolymer, in the polymeric matrix. In this case, the
rubbery block copolymer of formula (I) is preferably used as the
rubbery block copolymer. The especially preferred amount of the
rubbery block copolymer is not more than 10% by weight, and the
amount of the polystyrene resin is not more than 80% by weight,
both based on the polymeric matrix.
The high molecular resin composition of this invention comprises 97
to 99.9% by weight of a polymeric matrix containing polyphenylene
ether, such as the polyphenylene ether alone, or a mixture of the
polyphenylene ether with the polystyrene resin and/or rubbery
copolymer, and dispersed therein, 0.1 to 3% by weight of the olefin
oligomer having a number average molecular weight of not more than
about 10,000.
The olefin oligomer having such a low molecular weight used in this
invention is a brittle wax-like solid which when melted and
solidified, can be easily disintegrated by hand. Accordingly,
unlike high molecular polyolefins having a molecular weight of, for
example, more than 40,000 generally used in producing molded
articles such as films, the olefin oligomer by itself does not have
moldability and cannot be used as molding material.
It was quite unexpected that the inclusion of a minor proportion of
such a low-molecular-weight olefin oligomer improves the impact
strength and processability, especially the former, of a high
molecular resin composition containing polyphenylene ether.
The olefin oligomer used in this invention has a number averge
molecular weight of not more than about 10,000, preferably about
1,000 to about 10,000, more preferably about 1,000 to about 5,000.
Olefin oligomers having a number average molecular weight of more
than about 10,000 produce only a small effect of improving the
melt-processability of a resin composition containing polyphenylene
ether.
The amount of the olefin oligomer having a number average molecular
weight of not more than about 10,000 used in this invention is 0.1
to 3% by weight, preferably 0.1 to 1% by weight, based on the
polymer resin composition.
If the amount of the olefin oligomer is less than 0.1%, no marked
improvement in impact strength can be obtained. If it exceeds 3% by
weight, the olefin oligomer does not have sufficient compatibility
with the polymeric matrix containing polyphenylene ether, and
therefore, molded articles prepared from the high molecular resin
composition have poor surface condition. For example, surface gloss
is reduced to impair the aesthetic characteristics of the molded
articles. Furthermore, the various properties of the molded
articles are deteriorated.
When the olefin oligomer is used in an amount of 0.1 to 1% by
weight which is the preferred range, the properties and
processability of the high molecular resin composition are improved
with a good balance between them.
Preferred olefin oligomers are homo-oligomers or co-oligomers of
vinyl-type olefin monomers.
Examples of the olefin oligomers include (a) homo-oligomers of
vinyl-type olefin monomers such as ethylene, propylene or butylene,
(b) co-oligomers of the aforesaid vinyl-type olefin monomers with
each other, and (c) halogenated oligomers obtained by halogenation
of the homo-oligomers (a) or co-oligomers (b).
Examples of the homo-oligomers (a) are an ethylene oligomer
(homo-oligoethylene), homo-oligopropylene and homo-oligobutylene.
Examples of the co-oligomers (b) include an ethylene-propylene
co-oligomer, an ethylene-butylene co-oligomer, a propylene-butylene
co-oligomer, and an ethylene-propylene-butylene co-oligomer.
Examples of the halogenated oligomers (c) are halogenated products
of the specific oligomers or co-oligomers (a) and (b) listed above,
such as their fluorides and chlorides. Chloroethylene oligomer and
fluoroethylene oligomer are specific examples.
Among the aforesaid olefin oligomers, homo-oligoethylene,
homo-oligopropylene and an ethylene-propylene co-oligomer are
especially preferred. As stated hereinabove, these olefin oligomers
used in this invention have a number average molecular weight of
not more than about 10,000.
Conventional resin additives, such as plasticizers, stabilizers,
lubricants, flame retardants, pigments, dyes and fillers, may be
included into the polymeric matrix containing polyphenylene ether,
according to the uses of the resulting high molecular resin
composition.
The high molecular resin composition of this invention can be
easily produced by a known method of melt-mixing thermoplastic
resins. For example, a convenient method generally used comprises
mixing polyphenylene ether and, optionally the polystyrene resin
and/or rubbery polymer, with the olefin oligomer in predetermined
mixing proportions in a mixer, then fully kneading the resulting
mixture in a melt-extruder, and extruding the resultant uniform
melt to form pellets.
The following Examples illustrate the present invention in detail.
It should be noted that the invention is in no way limited by these
examples. In these Examples, all percentages (%) are by weight
unless otherwise specified.
EXAMPLE 1
High molecular resin compositions were prepared which contained
poly-2,6-dimethyl-1,4-phenylene ether having an intrinsic
viscosity, measured in chloroform at 30.degree. C., of 0.50 dl/g
and a low-molecular-weight ethylene oligomer having an average
molecular weight of about 2,000 (Sanwax 1519, a product of Sanyo
Chemical Ind. Co., Ltd.) in the amounts indicated in Table 1.
Each of these resin compositions was prepared by mixing
predetermined amounts of powdery poly-2,6-dimethyl-1,4-phenylene
ether and powdery ethylene oligomer in a mixer, melt-kneading the
mixture in a twin-screw extruder, and extruding the homogenous
mixture to form pellets.
The resulting pellets were molded in an injection molding machine
to form test specimens for the various tests shown in Table 1.
The results are shown in Table 1. In Table 1, and subsequent
tables, the content in weight percent of the ethylene oligomer is
based on the resulting high molecular resin composition.
TABLE 1
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Test item Izod impact Tensile Content strength impact Tensile
strength Surface condi- of Q-value of (notched; strength, (1/8
inch, Elonga- tion of the ethylene pellets 1/8 inch; 1/16 inch,
kg/cm.sup.2) tion at molded article oligomer (cm.sup.3 /sec.) kg
.multidot. S-type at at break (observed with Run No. (wt. %) (*1)
cm/cm) (kg .multidot. cm/cm.sup.2) yield break (%) the naked eye)
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1 0 3.6 .times. 10.sup.-3 4.0 400 740 660 90 Excellent 2 0.5 4.1
.times. 10.sup.-3 4.7 430 740 660 90 Excellent 3 1 4.6 .times.
10.sup.-3 5.3 450 740 660 90 Excellent 4 3 5.9 .times. 10.sup.-3
8.3 360 720 620 70 Good 5 5 10.5 .times. 10.sup.-3 11.5 60 -- (*2)
610 10 Poor
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(*1): Measured by a Kokatype flow tester. A nozzle, 1.phi. .times.
2 mm, was used, and the Qvalues are the extrusion speeds (cm.sup.3
/sec.) at 290.degree. C. and 60 kg/cm.sup.2. (*2): This shows that
the specimen broke before it reached a yield point.
EXAMPLE 2
High molecular resin compositions were prepared which contained a
polyphenylene ether copolymer composed of 95 mole% of
2,6-dimethylphenol and 5 mole% of 2,3,6-trimethylphenol and having
an intrinsic viscosity, measured in chloroform at 30.degree. C., of
0.50 dl/g, and a low-molecular-weight propylene oligomer having a
number average molecular weight of about 4,000 (Viscol 550P, a
product of Sanyo Chemical Ind. Co. Ltd.) in the amounts shown in
Table 2.
The preparation and molding of each of these resin compositions
were performed in the same way as in Example 1. The results are
shown in Table 2.
TABLE 2
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Test item Surface condition Tensile of the Izod impact impact
molded ar- Content of Q-value of strength, strength Tensile
strength Elonga- ticle (ob- propylene pellets notched (1/16 inch,
(1/8 inch, kg/cm.sup.2) tion at served with oligomer (cm.sup.3
/sec.) 1/8 inch S-type) at at break the naked Run No. (wt. %) (*1)
(kg .multidot. cm/cm) (kg .multidot. cm/cm.sup.2) yield break (%)
eye)
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1 0 3.9 .times. 10.sup.-3 3.9 400 750 660 90 Excellent 2 0.5 4.3
.times. 10.sup.-3 5.0 450 750 660 90 Excellent 3 1 4.7 .times.
10.sup.-3 6.0 510 740 680 90 Excellent 4 3 6.6 .times. 10.sup.-3
9.4 420 710 580 50 Good 5 5 8.5 .times. 10.sup.-3 13.9 40 -- (*2)
530 10 Poor
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(*1) and (*2): Same as the footnote to Table 1.
EXAMPLE 3
High molecular resin compositions were prepared which contained a
polymeric matrix consisting of 39% by weight of a polyphenylene
ether copolymer composed of 95 mole% of 2,6-dimethylphenol and 5
mole% of 2,3,6-trimethylphenol and having an intrinsic viscosity,
measured in chloroform at 30.degree. C., of 0.51 dl/g, 50% by
weight of rubber-modified high impact polystyrene (content of the
grafted rubber gel phase 13% by weight; the intrinsic viscosity of
the polystyrene matrix, measured in chloroform at 25.degree. C.,
was 0.89 dl/g), 4% by weight of a styrene-butadiene-styrene block
copolymer (containing an intermediate block of rubbery
polybutadiene, and polystyrene blocks at both ends; its 20% by
weight toluene solution showed a viscosity of 1500 c.p. when it was
measured by a Brookfield viscometer at 25.degree. C.), 6% by weight
of titanium oxide and 1% by weight of a stabilizer, and ethylene
oligomer having a number average molecular weight of about 2,000 in
the amounts shown in Table 3.
The preparation and molding of each of the high molecular resin
compositions were performed under the same conditions as in Example
1. The results obtained are shown in Table 3.
TABLE 3
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Test item Gloss of the sur- Izod impact Tensile strength face of
Content of Q-value of strength Tensile impact 1/8 inch Elonga- the
ethylene pellets (notched) strength, 1/16 (kg/cm.sup.2) tion at
molded oligomer (cm.sup.3 /sec) 1/8 inch inch, S-type at at break
article Run No. (wt. %) (*3) (kg .multidot. cm/cm) (kg .multidot.
cm/cm.sup.2) yield break (%) (*4)
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1 0 4.5 .times. 10.sup.-3 15 130 550 500 30 72 2 1 5.0 .times.
10.sup.-3 17 140 530 490 40 77 3 3 6.6 .times. 10.sup.-3 21 130 510
480 40 77 4 4.5 8.6 .times. 10.sup.-3 20 90 420 470 40 61
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(*3): Measured by a Kokatype flow tester. A nozzle, 1.phi. .times.
2 mm, was used, and the Qvalues are the extrusion speeds (cm.sup.3
/sec.) at 230.degree. C. and 60 kg/cm.sup. 2. (*4): Values measured
at an angle of incidence of 45.degree..
EXAMPLE 4
High molecular resin compositions were prepared which contained a
polymeric matrix consisting of 39% by weight of a polyphenylene
ether copolymer composed 95 mole% of 2,6-dimethylphenol and 5 mole%
of 2,3,6-trimethylphenol and having an intrinsic viscosity,
measured in chloroform at 35.degree. C., of 0.51 dl/g, 44.5% by
weight of rubber-modified high impact polystyrene, 2.5% by weight
of a styrene-butadiene-styrene block copolymer, 6% by weight of
titanium oxide, 0.5% by weight of a stabilizer and 7.5% by weight
of triphenyl phosphate, and ethylene oligomer having a number
average molecular weight of about 2,000 or propylene oligomer
having a number average molecular weight of about 4,000 in the
amounts shown in Table 4.
The preparation and molding of each of these high molecular resin
compositions were performed in the same way as in Example 1. The
results are shown in Table 4.
TABLE 4
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Test item Gloss of Tensile the sur- Izod impact impact Tensile
strength face of Content of Q-values of strength strength, 1/8inch
Elonga- the olefin pellets (notched) 1/16 inch, (kg/cm.sup.2) tion
at molded oligomer (cm.sup.3 /sec.) 1/8inch S-type at at break
article Run No. (wt. %) (*3) (kg . cm/cm) (kg . cm/cm.sup.2) yield
break (%) (*4)
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1 0 3.5 .times. 10.sup.-2 14 100 440 470 40 66 2 ethylene 4.0
.times. 10.sup.-3 18 130 440 490 30 75 oligomer (1) 3 propylene 4.0
.times. 10.sup.-3 18 150 440 470 40 80 oligomer (1)
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(*3) and (*4) are the same as the footnote to Table 3.
EXAMPLE 5
High molecular resin compositions were prepared which contained a
polymeric matrix consisting of 39% by weight of a polyphenylene
ether composed of 95 mole% of 2,6-dimethylphenol and 5 mole% of
2,3,6-trimethylphenol and having an intrinsic viscosity, measured
in chloroform at 30.degree. C., of 0.52 dl/g, 50% by weight of
rubber-modified high impact polystyrene, 3.5% by weight of a
styrene-butadiene-styrene block copolymer, 6.5% by weight of
titanium oxide and 1% by weight of a stabilizer, and ethylene
oligomer having a number average molecular weight of about 9,000
(Wax PE-190, a product of Hoechst AG) in the amounts indicated in
Table 5.
The preparation and molding of each of the high molecular resin
compositions were performed in the same way as in Example 1. The
results are shown in Table 5.
TABLE 5
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Test item Gloss Tensile of the Content of Izod impact impact
surface the ethyl- Q-value of strength strength, Tensile strength
Elonga- of the lene pellets (notched) 1/16 inch; 1/8 inch tion at
molded oligomer (cm.sup.3 /sec) 1/8 inch S-type (kg/cm.sup.2) break
article Run No. (wt. %) (*3) (kg .multidot. cm/cm) (kg .multidot.
cm/cm.sup.2) at yield at break (%) (*4)
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1 0 3.8 .times. 10.sup.-3 14 130 560 520 30 69 2 1 4.3 .times.
10.sup.-3 16 140 560 520 40 73 3 2 5.1 .times. 10.sup.-3 18 140 550
500 40 72
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(*3) and (*4) are the same as the footnote to Table 3.
* * * * *